Calcium carboxylate phenol derivative

ABSTRACT

A phenol derivative represented by the formula ##STR1## wherein R 1  is a secondary or tertiary hydrocarbon residue of having 3 to 8 carbon atoms, R 2  is a hydrocarbon residue having 1 to 12 carbon atoms, X is ##STR2## wherein R 3 , R 4  and R 5  each is an alkylene group having 1 to 4 carbon atoms, Z is an n-valent group and n is an integer of 1 to 8. 
     This compound is effective to prevent the oxidation of organic materials.

This is a division of application Ser. No. 584,636, filed Feb. 29, 1984,now U.S. Pat. No. 4,633,008.

FIELD OF THE INVENTION

The present invention relates to a novel phenol derivative. The compoundof this invention is effective to prevent the oxidation of variousorganic materials.

BACKGROUND OF THE INVENTION

Organic materials such as natural polymers, synthetic polymers, oils andfats, lubricating oils or hydraulic fluids, lose their usefulness whenoxidized. Therefore, various antioxidants have been devised to add tosuch organic materials. For example, it is known that hindered phenols,organic sulfur compounds, organic phosphorus compounds, and aromaticamines are effective antioxidants, which are used alone or incombination with each other. Examples of derivatives having the hinderedphenol skeleton are disclosed in Japanese Patent Publication Nos.2488/1958, 17164/1963, and 9651/1967. Those compounds are nowpractically used. Unexamined Published Japanese Patent Application Nos.59835/1972, 128656/1982, and 128679/1982 disclose hindered phenolderivatives as the antioxidants. These conventional antioxidantcompounds are not necessarily satisfactory under very severe conditions.

SUMMARY OF THE INVENTION

Accordingly, an object of this invention is to provide a specific phenolderivative to overcome the disadvantages in the conventional compounds.

The phenol derivative is the compound represented by formula (I)##STR3## wherein R¹ is a secondary or tertiary hydrocarbon residuehaving 3 to 8 carbon atoms, R² is a hydrocarbon residue having 1 to 12carbon atoms, X is ##STR4## wherein R³, R⁴, and R⁵ each is an alkylenegroup having 1 to 4 carbon atoms, Z is an n-valent group, and n is aninteger of 1 to 8.

The compound of formula (I) is effective to prevent the oxidation oforganic materials. The compound is also effective to prevent theoxidation of synthetic high molecular weight materials such aspolyolefin (e.g., polyethylene, polypropylene or ethylene-propylenecopolymer); polystyrene; polyvinyl chloride; and ABS resin, which areexposed under severe oxidizing conditions when they are molded and areused as the final products.

DETAILED DESCRIPTION OF THE INVENTION

The phenol derivative of this invention is represented by the formula(I) described above.

The group X is limited to bond to the specific position (i.e.,o-position) of the phenol nucleus, and is ##STR5##

Therefore, the formula (I) is, for the simplicity, represented by theformula (II) ##STR6## wherein R¹ is a secondary or tertiary hydrocarbonresidue having 3 to 8 carbon atoms, R² is an alkyl group having 1 to 12carbon atoms, R³ is an alkylene group having 1 to 4 carbon atoms, Z isan n-valent organic group, and n is an integer of 1 to 8 or the formula(III) ##STR7## wherein R¹ is a secondary or tertiary hydrocarbon residuehaving 3 to 8 carbon atoms, R² is a hydrocarbon residue having 1 to 12carbon atoms, R⁴ and R⁵ each is an alkylene group having 1 to 4 carbonatoms, Z is an n-valent group, and n is an integer of 1 to 8.

Phenol Derivatives Represented By Formula (II)

In the formula (II), R¹ is a secondary or tertiary hydrocarbon residuehaving 3 to 8 carbon atoms.

Examples of the hydrocarbon residues include isopropyl, isobutyl,tertiary butyl, secondary and tertiary pentyl, hexyl, heptyl, and octyl,which are of chain structure, and also include 1-methylcyclohexyl,1-phenylethyl, and norbornyl, which are of cyclic structure. Of these,the most preferred examples are tertiary butyl and 1-methylcyclohexyl.

R² is an alkyl group having 1 to 12 carbon atoms.

Example of the alkyl group include methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl, which are ofchain structure, and also include 1-methylcyclohexyl, 1-phenylethyl, andnorbornyl, which are of cyclic structure. Of these, preferred examplesas antioxidants are methyl and tertiary butyl.

R³ is an alkylene group having 1 to 4 carbon atoms.

Examples of the alkylene group include methylene, ethylene,trimethylene, propylene, tetramethylene, and ethylethylene (Theseexamples are applied to another alkylenes described below). Of these,the preferred example is ethylene.

Z is an n-valent organic group.

One group of Z is a hydrocarbon residue. Examples thereof include C₁-C₁₇ alkyl, C₁ -C₁₀ alkylene, C₃ -C₁₀ 3 to 8-valent aliphatichydrocarbon residue (e.g., 1,2,3-propanetriyl), phenyl,1,3,5-benzenetriyl, and 1,2,4,5-benzenetetrayl.

Another group of Z is a group containing sulfur atom(s). Examplesthereof include --R^(a) --S--R^(b) -- (wherein R^(a) and R^(b) each is aC₁ -C₁₀ alkylene, preferably R^(a) and R^(b) each is --CH₂ CH₂ --);R^(c) --S--R^(d))_(p) (wherein R^(c) is a p-valent hydrocarbon residue(e.g., 2 (or 3), 5 (or 6)-bicyclo[2.2.1]heptanediyl, 3 (or 4 or 5), 8(or 9)-tricyclo[5.2.1.0²,6 ]decanediyl, or cyclododecanetriyl, and R^(d)is each a C₁ -C₁₀ alkylene (preferably --CH₂ CH₂ --)); and ##STR8##(wherein R^(w) is a C₁ -C₁₀ alkylene).

Further group of Z is a group containing nitrogen atom(s). Examplesthereof include N--R^(e))₃ (wherein R^(e) each is a C₁ -C₁₀ alkylene,preferably R^(e) is all --CH₂ --).

Still another group of Z is a group containing oxygen atom(s). Examplesthereof include --R^(f) --O--R^(g) -- (wherein R^(f) and R^(g) each is aC₁ -C₁₀ alkylene, preferably --CH₂ --), C--R^(h) --O--R^(i) --₄ (whereinR^(h) and R^(i) each is a C₁ -C₁₀ alkylene, preferably R^(h) each is--CH₂ -- and R^(i) each is --CH₂ CH₂ --), and ##STR9## (wherein R^(j),R^(k), and R^(l) each is a C₁ -C₁₀ alkylene, preferably --CH₂ --, and qis an integer of 0 to 5).

Still further group of Z is a group containing at least two of sulfuratom, nitrogen atom, and oxygen atom. Examples thereof include ##STR10##(wherein R^(m), R^(o), and R^(p) each is a C₁ -C₁₀ alkylene),

    C--CH.sub.2 OCO--(CH.sub.2).sub.2 --S--R.sup.r --.sub.4

(wherein R^(r) is a C₁ -C₁₀ alkylene), ##STR11## (wherein R^(s) is a C₁-C₁₀ alkylene),

    O--CH.sub.2 C--CH.sub.2 OCOCH.sub.2 CH.sub.2 --S--R.sup.t --.sub.3 ].sub.2

(wherein R^(t) is a C₁ -C₁₀ alkylene), and ##STR12## (wherein R^(u) is aC₁ -C₁₀ alkylene).

The oxygen-containing Z includes a group formed by esterifying the 8hydroxyl groups in sucrose with --R^(v) --S--CH₂ CH₂ COO-- (whereinR^(v) is a C₁ -C₁₀ alkylene).

Of these, the most preferred group is a group represented by the formula##STR13##

Representative examples of the phenol derivative represented by theformula (II) are shown below. The numbers designating the compounds willbe referred to in the Examples and Application Examples described after.##STR14##Bis[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propyl]3,3'-thiodipropionate##STR15##Bis[3-(3-tert-butyl-5-ethyl-2-hydroxyphenyl)propyl]3,3'-thiodipropionate##STR16##Bis[3-(3-tert-butyl-2-hydroxy-5-isopropylphenyl)propyl]3,3'-thiodipropionate##STR17##Bis[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propyl]3,3'-thiodipropionate##STR18##Bis[3-(3-tert-butyl-2-hydroxy-5-nonylphenyl)propyl]3,3'-thiodipropionate##STR19##Bis[3-(3-tert-butyl-2-hydroxy-5-dodecylphenyl)propyl]3,3'-thiodipropionate##STR20##Bis[3-(2-hydroxy-3-isopropyl-5-methylphenyl)propyl]3,3'-thiodipropionate##STR21##Bis[3-[2-hydroxy-3-(1-methylcyclohexyl)-5-methylphenyl)]propyl]3,3'-thiodipropionate##STR22##Bis[2-(3-tert-butyl-2-hydroxy-5-methylphenyl)ethyl]3,3'-thiodipropionate##STR23##Bis[4-(3-tert-butyl-2-hydroxy-5-methylphenyl)butyl]3,3'-thiodipropionate##STR24##Bis[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propyl]heptanedioate##STR25##Bis[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propoxycarbonylmethyl]ether##STR26## 3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propyl octadecanoate##STR27## 3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propyl3-[3-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy]propylthio]propionate##STR28##Tris[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propoxycarbonylmethyl]amine##STR29##Tris[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propyl]1,2,3-propanetricarboxylate##STR30##Tris[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propyl]1,2,3-propanetricarboxylate##STR31##Tetrakis[2-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propoxycarbonyl]ethyloxymethyl]methane##STR32##Tetrakis[2-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propoxycarbonyl]ethyloxymethyl]methane##STR33##1,3,5-tris[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propoxycarbonyl]benzene##STR34##1,2,4,5-tetrakis[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propoxycarbonyl]benzene##STR35##1,3,5-tris[3-[2-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propoxycarbonyl]ethylthio]propyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione##STR36##1,3,5-tris[3-[2-[3-[2-hydroxy-3-(1-methylcyclohexyl)-5-methylphenyl]propyloxycarbonyl]ethylthio]propyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione##STR37##1,3,5-tris[3-[2-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propoxycarbonyl]ethylthio]propyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione##STR38## 2(or 3),5(or6)-bis[2-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propoxycarbonyl]ethylthio]bicyclo[2.2.1]heptane##STR39## 3(or 4 or 5),8(or9)-bis[2-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propoxycarbonyl]ethylthio]tricyclo[5.2.1.0²,6]decane ##STR40##Tris[2-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propoxycarbonyl]ethylthio]cyclododecane##STR41##Tris[2-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propoxycarbonyl]ethylthio]cyclododecane##STR42##Tetrakis[3-[4-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propoxycarbonyl]butylthio]propionyloxymethyl]methane##STR43##Tetrakis[3-[4-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propoxycarbonyl]butylthio]propionyloxymethyl]methane##STR44##Bis[2-[2,4-bis[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propoxycarbonyl]butylthio]ethyl]ether##STR45##Bis[2,4-bis[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propoxycarbonyl]butyl]sulfide##STR46## Hexakisester of dipentaerythritol and3-[4-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propoxycarbonyl]butylthio]propionicacid ##STR47## Octakisester of sucrose and3-[4-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propoxycarbonyl]butylthio]propionicacid

Synthesis of Compound (II)

The compound (II) of this invention can be synthesized in any manner byintroducing or forming specific groups or linkages.

The representative example of the synthesis is the reaction of analcohol of the formula (IV) shown below with a carboxylic acid of theformula (V) shown below under the ester formation conditions. ##STR48##wherein R¹, R², R³, Z, and n each is the same as defined in the formula(II) above.

"Reaction under the ester formation condition" means that the twocompounds are reacted directly, preferably in the presence of anesterification catalyst; the carboxylic acid is reacted in the form ofits active derivative such as acid halide, acid anhydride or acid-loweralkyl ester; or the alcohol is reacted in the form or its activederivative such as lower carboxylic acid ester.

In the case where a carboxylic acid is used, the esterification reactionis carried out in an inert solvent in the presence of an acid catalyst.Examples of the acid catalyst include sulfuric acid, p-toluenesulfonicacid, and strongly acidic ion exchange resin. Examples of the reactionsolvent include aliphatic hydrocarbons such as n-pentane, n-hexane, andn-heptane; alicyclic hydrocarbons such as cyclohexane; and aromatichydrocarbons such as benzene, toluene, and xylene. In order to increasethe rate of ester formation, the water formed by the reaction isdischarged from the reaction system by azeotropy using an inert solvent.

In the case where an acid-lower alkyl ester is used, the ester exchangereaction is carried out in an inert organic solvent in the presence of astrong base under heating, while discharging the lower alcohol formed bythe reaction from the reaction system. Examples of the reaction solventinclude amides such as dimethylformamide, dimethylacetamide, andhexamethylphosphonamide, and organic solvents such as toluene anddimethylsulfoxide. Examples of the strong base include strongly basicalkali metal compounds such as sodium methylate, sodium ethylate,potassium hydroxide, and sodium amide; and titanate compounds such astetraisopropyl or tetrabutyl titanate. The reaction smoothly proceeds byheating at 30° to 180° C.

In the case where an acid halide is used, the reaction is carried out at0° to 130° C., preferably 20° to 70° C., in the presence of a hydrogenhalide acceptor in an inert solvent. Examples of the hydrogen halideacceptor include pyridine, triethylamine, dimethylaniline, andtetramethyl urea. Examples of the inert solvent include aliphatichydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons suchas cyclohexane; aromatic hydrocarbons such as benzene and xylene; andethers such as diethyl ether and tetrahydrofuran.

In the case where an acid anhydride is used, the reaction is carried outin an inert solvent, or is carried out with an excess of the acidanhydride in the absence of an inert solvent. Examples of the inertsolvent include aromatic hydrocarbons such as benzene, toluene, andxylene; and ether compounds such as diethyl ether and tetrahydrofuran.

Phenol Derivatives Represented By Formula (III)

In the formula (III), R¹ and R² each is the same as defined in theformula (II), and R⁴ and R⁵ each is an alkylene having 1 to 4 carbonatoms such as methylene, ethylene, and ethylethylene. The most preferredexample for R⁴ is trimethylene and the most preferred example for R⁵ isethylene.

Z is an n-valent group.

One group of Z is a metal. Examples of the metal include sodium,potassium, calcium, magnesium, zinc, nickel, and aluminum.

Another group of Z is a hydrocarbon residue. Examples thereof include C₁-C₁₈ alkyl, C₁ -C₁₀ alkylene, C₃ -C₁₀ 3 to 4-valent aliphatichydrocarbon residue (e.g., 1,2,3-propanetriyl,2,2-dimethylbutane-1,1',1"-triyl, and neopentanetetrayl), phenyl,phenylene, and 1,3,5-benzenetriyl.

Further group of Z is a group containing sulfur atom(s). Examplesthereof include --R^(a) --S--R^(b) -- (wherein R^(a) and R^(b) each is aC₁ -C₁₀ alkylene, preferably R^(a) and R^(b) each is --CH₂ CH₂ --).

Still another group of Z is a group containing nitrogen atom(s).Examples thereof include N--R^(c))₃ (wherein R^(c) is a C₁ -C₁₀alkylene) and 2,2,6,6-tetramethyl-4-piperidyl.

Still further group of Z is a group containing oxygen atom(s). Examplesthereof include --R^(d) --OR^(e))_(m) (wherein m is an integer of 1 to3; R^(d) and R^(e) each is a C₂ -C₃ alkylene), O--CH₂ --C(CH₂ --]₃, andsucrose from which the hydroxyl groups are removed.

Yet further group of Z is a group containing both nitrogen and oxygenatoms. Examples thereof include the group of the formula ##STR49##

In formula (III), n is an integer of 1 to 8.

Representative examples of the phenol derivatives represented by theformula (III) are shown below. The numbers designating the compoundswill be referred to in Examples described below. ##STR50## Sodium3-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propylthio]propionate##STR51## Calciumbis[3-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propylthio]propionate]##STR52## Calciumbis[3-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propylthio]propionate]##STR53## Aluminumtris[3-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propylthio]propionate]##STR54## Methyl3-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propylthio]propionate##STR55## Methyl3-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propylthio]propionate ##STR56##Methyl3-[3-(2-hydroxy-5-methyl-3-(1-methylcyclohexyl)phenyl)propylthio]propionate##STR57## Ethyl3-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propylthio]propionate##STR58## Octadecyl3-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propylthio]propionate##STR59## Octadecyl3-[3-(2-hydroxy-3-isopropyl-5-methylphenyl)propylthio]propionate##STR60## Octadecyl3-[3-[2-hydroxy-5-methyl-3-(1-methylcyclohexyl)phenyl]propylthio]propionate##STR61## Octadecyl3-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propylthio]propionate ##STR62##Octadecyl3-[3-[5-tert-butyl-2-hydroxy-3-(1-methylcyclohexyl)phenyl]propylthio]propionate##STR63## Octadecyl3-[3-[2-hydroxy-3,5-bis(1-methylcyclohexyl)phenyl]propylthio]propionate##STR64## Phenyl3-(3-tert-butyl-5-ethyl-2-hydroxyphenylmethylthio)butyrate ##STR65##Methyl3-[3-(3-tert-butyl-2-hydroxy-5-isopropylphenyl)propylthio]-2-methylpropionate##STR66## 2,2,6,6-tetramethyl-4-piperidinyl4-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propylthio]butyrate ##STR67##2,2,6,6-tetramethyl-4-piperidinyl3-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propylthio]propionate##STR68## Cyclohexyl3-[3-(3-tert-butyl-2-hydroxy-5-nonylphenyl)propylthio]propionate##STR69## Ethylenebis[3-[3-(3-tert-butyl-2-hydroxy-4-methylphenyl)propylthio]propionate]##STR70## Ethylenebis[3-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propylthio]propionate]##STR71##1,2,3-tris[3-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propylthio]propionyloxy]propane##STR72##Tetrakis[3-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propylthio]propionyloxymethyl]methane##STR73##Tetrakis[3-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propylthio]propionyloxymethyl]methane##STR74##Tetrakis[3-[3-[2-hydroxy-5-methyl-3-(1-methylcyclohexyl)phenyl]propylthio]propionyloxymethyl]methane##STR75##Tetrakis[3-[3-[2-hydroxy-3,5-bis(1-methylcyclohexyl)phenyl]propylthio]propionyloxymethyl]methane##STR76##1,1,1-tris[3-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propylthio]propionyloxymethyl]propane##STR77##1,1,1-tris[3-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propylthio]propionyloxymethyl]propane##STR78##1,1,1-tris[3-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propylthio]propionyloxymethyl]ethane##STR79##1,1,1-tris[3-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propylthio]propionyloxymethyl]ethane##STR80##1,3,5-tris[3-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propylthio]propionyloxy]benzene##STR81##Bis[2-[3-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propylthio]propionyloxy]ethyl]sulfide##STR82##Tris[2-[3-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propylthio]propionyloxy]ethyl]amine##STR83##Bis[2-[3-[3-(3,5-di-tert-butylphenyl)propylthio]propionyloxy]ethyl]ether##STR84##Bis[2,2,2-tris[3-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propylthio]propionyloxymethyl]ethyl]ether##STR85##Bis[2,2,2-tris[3-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propylthio]propionyloxymethyl]ethyl]ether##STR86##Bis[2,2,2-tris[3-[3-(2-hydroxy-5-methyl-3-(1-methylhexyl)phenyl]propylthio]propionyloxymethyl]ethyl]ether##STR87## Octakisester of sucrose and3-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propylthio]propionic acid##STR88##1,3,5-tris[2-[3-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propylthio]propionyloxy]ethyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione

Synthesis of Phenol Derivatives Represented By Formula (III)

The compound (III) of this invention can be produced in any manner byintroducing or forming specific groups or linkages, as exemplifiedbelow.

(1) In the case where Z is a metal, the compound can be produced byreacting a hydroxide, carbonate or bicarbonate containing the metal witha carboxylic acid represented by formula (VI) ##STR89## wherein R¹ is asecondary or tertiary hydrocarbon group residue having 3 to 8 carbonatoms; R² is a hydrocarbon residue having 1 to 12 carbon atoms; and R⁴and R⁵ each is an alkylene group having 1 to 4 carbon number 1 to 4.

The reaction to synthesize a metal salt of carboxylic acid is carriedout at 0° to 100° C., preferably 10° to 40° C., in water or an inertorganic solvent. Examples of the inert organic solvent include polarsolvents such as dimethylformamide, dimethylacetamide,hexamethylphosphonamide, and dimethylsulfoxide.

(2) In the case where Z is an organic group, the compound can beproduced by reacting a compound represented by the formula (VII)

    (HO).sub.n Z                                               (VII)

wherein n is an integer of 1 to 8, with a carboxylic acid represented bythe formula (VI) above or an active derivative thereof (acid-lower alkylester, acid halide, or acid anhydride).

The esterification reaction using a carboxylic acid is carried out in aninert organic solvent in the presence of an acid catalyst, or in excessof the compound of the formula (VII) in the absence of an inert organicsolvent. Examples of the acid catalyst include sulfuric acid,p-toluenesulfonic acid, and strongly acidic ion exchange resin. Examplesof the inert organic solvent include aliphatic hydrocarbons such asn-pentane, n-hexane, and n-heptane; alicyclic hydrocarbons such ascyclohexane; and aromatic hydrocarbons such as benzene, toluene, andxylene. In the case where an inert organic solvent is used, the waterformed by the reaction is discharged from the reaction system byazeotropy using an inert organic solvent to increase the rate of esterformation.

The ester exchange reaction using an acid-lower alkyl ester is carriedout under heating in an inert organic solvent in the presence of astrong base, while discharging the lower alcohol formed by the reactionfrom the reaction system. Examples of the inert organic solvent includeamides such as dimethylformamide, dimethylacetamide orhexamethylphosphonamide, and organic solvents such as toluene ordimethylsulfoxide. Examples of the strong base include strongly basicalkali metal compounds such as sodium methylate, sodium ethylate,potassium hydroxide or sodium amide, and titanate compounds such astetraisopropyl or tetrabutyl titanate. The reaction is suitably carriedout by heating at 30° to 180° C.

The reaction using an acid halide is carried out at 0° to 130° C.,preferably 20° to 70° C., in an inert solvent in the presence of ahydrogen halide acceptor. Examples of the hydrogen halide acceptorinclude pyridine, triethylamine, dimethylaniline, and tetramethyl urea.Examples of the inert solvent include aliphatic hydrocarbons such asn-hexane or n-heptane; alicyclic hydrocarbons such as cyclohexane;aromatic hydrocarbons such as benzene, toluene or xylene; and ethercompounds such as diethyl ether or tetrahydrofuran.

The esterification reaction using an acid anhydride is carried out in aninert solvent, or in excess of the acid anhydride in the absence of aninert solvent. Examples of the inert solvent include aromatichydrocarbons such as benzene, toluene or xylene; and ether compoundssuch as diethyl ether or tetrahydrofuran.

Application of the Compound

The phenol derivative of this invention represented by the formula (I)is effective to prevent the oxidation of organic materials as describedbelow.

The phenol derivative of this invention as an antioxidant is effectiveto various organic materials. It is particularly useful when such isadded to synthetic high molecular weight materials.

The amount of the phenol derivative of this invention as an antioxidantvaries depending on the type, nature, and purpose of use of the organicmaterials such as rubber or resin to be stabilized. The amount isgenerally about 0.001 to 10 wt% based on the weight of the organicmaterial. For most applications, it is used in an amount of about 0.01to about 5 wt%. For example, 0.01 to 2.0 wt% for polyolefins, 0.01 to1.0 wt% for polyvinyl chloride and polyvinylidene chloride, 0.1 to 2.0wt% for polyethers, 0.3 to 3 wt% of polyurethane, and 0.01 to 1.0 wt%for polyester and polyamide.

The phenol derivative of this invention represented by the formula (I)is sufficiently effective as an antioxidant even when it is used alone,but the effect can be enhanced when used in combination with otherantioxidants such as sulfur type antioxidant, phosphorus typeantioxidant, phenol antioxidant, benzophenone type UV light absorber,benzotriazole type UV light absorber, hindered-amine type lightstabilizer, organo-nickel type light stabilizer, metal type deactivator,filler deactivator or metal soap. It can also be used in theconventional manner in combination with adjuvants such as antistaticagent, flame retardant, anti-fogging agent, voltage stabilizer,crosslinking agent, slip agent or colorant.

The compounds obtained in the following Examples 1 to 17 are the phenolderivatives represented by the formula (II), and the compounds obtainedin the following Examples 18 to 38 are the phenol derivativesrepresented by formula (III).

EXAMPLE 1Bis[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propyl]3,3'-thiodipropionate(Illustrative Compound No. 1)

Into a 30 ml four-neck flask equipped with a Dian-Stark trap werecharged 1.28 g (7.20 mmol) of 3,3'-thiodipropionic acid, 4.00 g (17.99mmol) of 3-(3-tert-butyl-2-hydroxy-5-methylphenyl)-1-propanol, 10 ml oftoluene and 0.27 g (1.4 mmol) of p-toluenesulfonic acid hydrate,followed by heating and refluxing for 2 hours under a nitrogen stream.After the completion of the reaction, diethyl ether was added and thereaction product was washed with water. The reaction product was thenwashed with saturated aqueous solution of sodium chloride and dehydratedwith anhydrous sodium sulfate. The organic solvent was removed underreduced pressure. After separation by silica gel column chromatography(solvent: chloroform), 2.67 g (4.55 mmol) of the desired product wasobtained. The yield was 63%. The physical properties of the product areshown below.

(1) ¹ H-NMR CDCl₃ δ[ppm] 1.40 (18H, s), 2.25 (6H, s), 1.50-3.20 (16H,m), 4.10 (4H, t), 5.05 (2H, s), 6.72 (2H, d), 6.88 (2H, d).

(2) IR: NaCl wavenumber [cm⁻¹ ] 3500, 2950, 1720, 1595, 1440, 1170, 860.

(3) MS: m/e (relative intensity) 586 (10, M⁺), 204 (100), 189 (70), 161(20).

EXAMPLES 2 TO 9

The compounds as shown in Table 1 were synthesized according to themethod used in Example 1. Their structures were confirmed by means ofNMR spectrums, IR spectrums and MS spectrums.

                                      TABLE 1                                     __________________________________________________________________________                              Reaction product                                    Reactants                 Illus-                                              Carboxylic acid           trated                                              Ex-                                                                              Compound  Alcohol      com-                                                                              Yield                                           am-                                                                              of Formula                                                                          (g) Compound of                                                                            (g) pound                                                                             (g) Yield                                                                             Physical properties of reaction                                               product                                 ple                                                                              (V)   (mmol)                                                                            Formula (IV)                                                                           (mmol)                                                                            No. (mmol)                                                                            (%) .sup.1 H--NMR CDCl.sub.3 δ                                              (ppm)        IR    MS                   __________________________________________________________________________    2  3,3'-thiodi-                                                                        1.08                                                                              3-(3,5-di-tert-                                                                        4.00                                                                               4  3.91                                                                              96  1.31(18H,s) 1.54(18H,s),                                                                   3500,                                                                               670(1,M.sup.+)          propionic                                                                           (6.05)                                                                            butyl-2-hydroxy-                                                                       (15.1)  (5.83)  1.60-2.40(4H,m), 2.40-                                                                     1730,                                                                               246(30),                acid      phenyl)-1-prop-          3.30(12H,m), 4.17(4H,t),                                                                   1200,                                                                               231(100).                         anol                     4.90(2H,bs), 6.96(2H,d),                                                      7.15(2H,d).                             3  Heptanedi-                                                                          1.15                                                                              3-(3-tert-butyl-                                                                       4.00                                                                              11  3.00                                                                              73  1.41(18H,s), 1.50-2.90                                                                     3490,                                                                               568(2,M.sup.+)          oic acid                                                                            (7.20)                                                                            2-hydroxy-5-me-                                                                        (17.99) (5.27)  (18H,m), 2.25(6H,s),                                                                       1720,                                                                               204(100),                         thylphenyl)-1-           4.10(4H,t), 5.05(2H,s),                                                                    1200,                                                                               189(70),                          propanol                 6.75(2H,d), 6.90(2H,d).                                                                          161(30).             4  Diglycolic                                                                          0.97                                                                              3-(3-tert-butyl-                                                                       4.00                                                                              12  2.72                                                                              70  1.40(18H,s), 1.50-2.90                                                                     3540,                                                                               5420,                   acid  (7.20)                                                                            2-hydroxy-5-me-                                                                        (17.99) (5.01)  (8H,m), 2.23(6H,s),                                                                        1740,                                                                               (0.1,M.sup.+)                     thylphenyl)-1-           4.24(4H,t), 4.24(4H,s),                                                                    1210,                                                                               204(100),                         propanol                 4.70(2H,s), 6.75(2H,d),                                                                    855.  189(85)                                                    6.90(2H,d).        161(20).              5*                                                                              Nitrilotri-                                                                         1.03                                                                              3-(3-tert-butyl-                                                                       4.50                                                                              15  2.72                                                                              63  1.40(27H,s), 1.50-2.90                                                                     3500,                                                                               806(10),                acetic acid                                                                         (5.40)                                                                            2-hydroxy-5-me-                                                                        (20.20) (3.38)  (12H,m), 2.23(9H,s),                                                                       1740,                                                                               554(10),                          thylphenyl)-1-           3.70(6H,s), 4.19(6H,t),                                                                    1260,                                                                               204(60),                          propanol                 5.15(3H,bs), 6.75(3H,d),                                                                   1100,                                                                               189(100),                                                  6.90(3H,d).  800.  161(35).             6  1,2,3-pro-                                                                          0.95                                                                              3-(3-tert-butyl-                                                                       4.00                                                                              16  2.90                                                                              68  1.40(27H,s), 1.40-3.00                                                                     3500,                                                                               789(1,M.sup.+)          panetricar-                                                                         (5.40)                                                                            2-hydroxy-5-me-                                                                        (17.99) (3.68)  (17H,m), 2.21(9H,s),                                                                       1720,                                                                               204(100),               boxylic   thylphenyl)-1-           4.17(6H,m), 5.04(2H,s),                                                                    1170,                                                                               189(70),                acid      propanol                 5.30(1H,s), 6.70(3H,d),                                                                          177(20),                                                   6.88(3H,d).        161(20),                                                                      149(20),                                                                      57(15).              7  Tetrakis(2-                                                                         1.72                                                                              3-(3-tert-butyl-                                                                       4.00                                                                              18  1.21                                                                              24  1.40(36H,s), 1.50-2.90                                                                     3500, 2950,                   carboxyeth-                                                                         (4.05)                                                                            2-hydroxy-5-me-                                                                        (17.99) (0.97)  (24H,m), 2.25(12H,s),                                                                      1720, 1595,                   yloxymeth-                                                                              thylphenyl)-1-           3.34(8H,s), 3.60(8H,t),                                                                    1170, 1110,                   yl)methane                                                                              propanol                 4.10(8H,t), 5.16(4H,s),                                                                    860.                                                             6.72(4H,d), 6.89(4H,d).                 8  Tris(2-car-                                                                         2.16                                                                              3-(3-tert-butyl-                                                                       3.00                                                                              27  2.19                                                                              45  1.40(27H,s), 1.20-3.40                                                                     3480, 2950,                   boxyethyl-                                                                          (4.50)                                                                            2-hydroxy-5-me-                                                                        (13.49) (2.00)  (39H,m), 2.25(9H,s),                                                                       1730, 1590,                   thio)cyclo-                                                                             thylphenyl)-1-           4.15(6H,t), 5.00(3H,s),                                                                    1270, 855.                    dodecane  propanol                 6.74(3H,d), 6.87(3H,d).                 9  Tetrakis [3-                                                                        2.91                                                                              3-(3-tert-butyl-                                                                       4.37                                                                              29  2.33                                                                              42  1.40(36H,s), 1.10-3.40                                                                     3500, 2940,                   (4-carboxy-                                                                         (3.27)                                                                            2-hydroxy-5-me-                                                                        (19.65) (1.36)  (64H,m), 2.25(12H,s),                                                                      1730, 1590,                   butylthio)-                                                                             thylphenyl)-1-           4.10(8H,t), 4.15(8H,s),                                                                    1170, 855.                    propionyl-                                                                              propanol                 5.16(4H,s), 5.16(4H,s),                    oxymethyl]-                        6.75(4H,d), 6.88(4H,d).                    methane                                                                    __________________________________________________________________________     *Hydrated ptoluenesulfonic acid was used in an amount of 2.46 g (12.95        mmol), which is not a catalytic amount, so that all of it is not caught b     nitrilotriacetic acid.                                                        IR: KBr tablet or NaCl; wavenumber (cm.sup.-1)                                MS: m/e (relative intensity)                                             

EXAMPLE 101,3,5-tris[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propoxycarbonyl]benzene(Illustrative Compound No. 20)

Into a 100 ml reactor equipped with a condenser, thermometer andnitrogen introducing thin tube were charged 1.54 g (6.00 mmol) oftrimethyl 1,3,5-benzenetricarboxylate, 4.00 g (18.00 mmol) of3-(3-tert-butyl-2-hydroxy-5-methylphenyl)-1-propanol and 20 ml ofN,N-dimethylformamide. The pressure of the reaction system was reducedto 20 mmHg and 75 vol% (15 ml) of N,N-dimethylformamide was distilledaway to dry the reactants, solvent and apparatus. The reaction systemwas cooled to room temperature, and the vacuum was broken by introducingdry nitrogen. 0.07 g (1.8 mmol) of sodium amide was immediately added toinitiate the ester exchange reaction. The reaction system was heated at50° to 60° C. under 20 mmHg for 2 to 3 hours, and then heated at 60° to80° C. under 20 mmHg for 2 to 3 hours while distillingN,N-dimethylformamide. Thereafter, the reaction mixture was furtherheated at 100° to 120° C. under 5 mmHg for 2 to 3 hours. When thereaction was completed, the reaction product was neutralized with dilutehydrochloric acid and then chloroform was added. After liquid separationand dehydration with anhydrous sodium sulfate, the organic solvent wasremoved under reduced pressure. After separation by silica gelchromatography (solvent: chloroform), 2.60 g (3.16 mmol) of the desiredproduct was obtained. The yield was 53%. The physical properties of theproduct are shown below.

(1) ¹ H-NMR CDCl₃ δ[ppm]1.40 (27H, s), 1.80-3.10 (12H, m), 2.23 (9H, s),4.40 (6H, t), 5.05 (3H, s), 6.78 (3H, d), 6.87 (3H, d), 8.76 (3H, s).

(2) IR: NaCl wavenumber [cm⁻¹ ] 3490, 2940, 1725, 1600, 1240, 850, 735.

EXAMPLES 11 TO 16

The compounds as shown in Table 2 were synthesized according to themethod used in Example 10. Their structures were confirmed by means ofNMR spectrums, IR spectrums and MS spectrums.

                                      TABLE 2                                     __________________________________________________________________________                                  Reaction product                                                              Illus-                                          Reactants                     trated       Physical properties of             Ex-                                                                              Methyl carboxylate                                                                          Alcohol      com-                                                                              Yield    reaction product                   am-                                                                              Compound of                                                                            (g)  Compound of                                                                            (g) pound                                                                             (g)  Yield                                                                             .sup.1 H--NMR CDCl.sub.3           ple                                                                              Formula (a)                                                                            (mmol)                                                                             Formula (IV)                                                                           (mmol)                                                                            No. (mmol)                                                                             (%) δ(ppm)                                                                             IR    MS                __________________________________________________________________________    11 Tetramethyl                                                                            1.72 3-(3-tert-butyl-                                                                        4.45                                                                             21  2.50 47  1.40(36H,s) 1.80-3.00                                                                    3510, 2940,                1,2,4,5-ben-                                                                           (5.00)                                                                             2-hydroxy-5-                                                                           (20.00) (2.33)   (16H,m), 2.21(12H,s),                                                                    1720, 1590,                zenetetra-    methylphenyl)-1-          4.40(8H,t), 5.25(4H,s),                                                                  1250, 855.                 carboxylate   propanol                  6.75(4H,d), 6.86(4H,d),                                                       8.06(2H,d).                        12 1,3,5-tris-                                                                            3.66 3-(3-tert-butyl-                                                                        4.00                                                                             22  2.97 42  1.40(27H,s),                                                                             3500, 2950,                [3-[2-(meth-                                                                           (6.00)                                                                             2-hydroxy-5-                                                                           (17.99) (2.52)   (36H,m), 2.25(9H,s),                                                                     1730, 1690,                oxycarbonyl)- methylphenyl)-1-          3.80-4.40(12H,m),                                                                        1590, 1220,                ethylthio]-   propanol                  (3H,s), 6.75(3H,d),                                                                      1170, 860.                 propyl]-                                6.86(3H,d).                           1,3,5-tri-                                                                    azine-2,4,6                                                                   (1H, 3H, 5H)--                                                                trione                                                                     13 1,3,5-tris-                                                                            3.66 3-[2-hydroxy-3-                                                                         4.72                                                                             23  3.44 44  1.30(9H,s), 1.27-3.17                                                                    3500, 2950,                [3-[2-(meth-                                                                           (6.00)                                                                             (1-methylcyclo-                                                                        (18.00) (2.64)   (66H,m), 2.23(9H,s),                                                                     1730, 1690,                oxycarbonyl)- hexyl)-5-methyl-          3.8-4.40(12H,m),                                                                         1590, 1220,                ethylthio]-   phenyl]-1-pro-            (3H,s), 6.67(3H,d),                                                                      1170, 855.                 propyl]-      panol                     6.87(3H,d).                           1,3,5-tri-                                                                    azine-2,4,6                                                                   (1H, 3H, 5H)--                                                                trione                                                                     14 2 or 3,5 or                                                                            5.94 3-(3-tert-butyl-                                                                        7.95                                                                             25  8.93 70  1.03(18H,s),                                                                             3500, 2900                 6-bis[2- (17.88)                                                                            2-hydroxy-5-                                                                           (35.76) (12.52)  2.13(6H,s),                                                                              1730, 1590,                (methoxycarbon-                                                                             methylphenyl)-1-          1.02-3.20(26H,m),                                                                        855.                       yl)ethylthio]-                                                                              propanol                  4.05(4H,t), 5.00(2H,s),               bicyclo-                                6.70(2H,d), 6.85(2H,d).               [2.2.1]-                                                                      heptane                                                                    15 Bis[2-[2,4-                                                                            5.51 3-(3-tert-butyl-                                                                       12.70                                                                             31  3.30 23  1.27(36H,s),                                                                             3500, 2900                 bis(methoxy-                                                                           (11.40)                                                                            2-hydroxy-5-                                                                           (57.10) (2.65)   2.10(12H,s),                                                                             1730, 1590,                carbonyl)-    methylphenyl)-1-          1.10-3.10(34H,m),                                                                        1160, 855.                 butylthio]-   propanol                  (4H,t), 4.10(8H,m),                   ethyl]ether                             4.90(2H,s), 5.03(2H,s),                                                       6.67(4H,d), 6.82(4H,d).            16 Bis[2,4-bis-                                                                           2.20 3-[2-hydroxy-3-                                                                         5.00                                                                             32  2.90 49  1.45(36H,s),                                                                             3500, 2950,                (ethoxycar-                                                                            (5.10)                                                                             (1-methylcyclo-                                                                        (22.50) (2.50)   (30H,m), 2.29(12H,s),                                                                    2860, 1730,                bonyl)butyl]- hexyl)-5-methyl-          4.00-4.45(8H,m),                                                                         1590, 1480,                sulfide       phenyl]-1-pro-            (4H,s), 6.80(4H,s),                                                                      1190, 1125,                              panol                     6.95(4H,s).                                                                              875.                    __________________________________________________________________________     Formula (a)                                                                   ##STR90##                                                                     IR: KBr tablet or NaCl; wavenumber                                            MS: m/e (relative intensity)                                             

EXAMPLE 17 3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propyl3-[3-(2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy]propylthio]propionate(Illustrative Compound No. 14)

Into a 50 ml reactor were charged 3.40 g (15.29 mmol) of3-(3-tert-butyl-2-hydroxy-5-methylphenyl)-1-propanol, 20 ml of diethylether and 1.94 g (16.00 mmol) of N,N-dimethylaniline. The atmosphere inthe reactor was replaced with dry nitrogen. To the reactants was addeddropwise 7.09 g (16.00 mmol) of3-[3-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]propylthio]propionylchloride. The reactants were heated and refluxed for 6 hours in thenitrogen stream. After the completion of the reaction, diethyl ether wasadded and the reaction product was neutralized with 10% sulfuric acid.After liquid separation, washing with saturated aqueous solution ofsodium chloride and dehydration with anhydrous sodium sulfate, theorganic solvent was removed under reduced pressure. After separation bysilica gel chromatography (solvent: chloroform), 6.42 g (10.20 mmol) ofthe desired product was obtained. The yield was 67%. The physicalproperties of the product are shown below.

(1) ¹ H-NMR CDCl₃ δ[ppm] 1.30 (27H, s), 1.50-2.30 (4H, s), 2.13 (3H, s),2.30-3.00 (12H, m), 4.06 (4H, t), 4.95 (1H, s), 5.03 (1H, s), 9.67 (1H,d), 9.87 (1H, d), 9.88 (2H, s).

(2) IR: NaCl wavenumber [cm⁻¹ ] 3630, 3500, 2940, 1730, 1590, 1230,1160, 870.

(3) MS: m/e (relative intensity) 628 (5, M⁺), 424 (10), 204 (100), 189(40), 161 (10), 147 (15), 57 (30).

The following Application Examples 1 to 16 demonstrate the antioxidantaction of the compound (II) of this invention.

APPLICATION EXAMPLES 1 TO 11 AND COMPARATIVE APPLICATION EXAMPLES 1 TO 3

0.10 wt% of the antioxidant as shown in Table 3 was added to apolypropylene powder having an intrinsic viscosity of 1.9 (measured intetralin at 135° C.) and an isotactic index of 98%, followed by thoroughmixing by a mixer. The polypropylene powder was pelletized by meltmixing using a 20 mm diameter extruder (L/D: 20) at a cylindertemperature of 260° C. The MFR (at 230° C.) of the pellets was measuredaccording to JIS K6758. The measured value was designated as MFR₁. Thepelletizing process was repeated three times under the same conditionsas above, and the MFR (at 230° C.) of the resulting pellets wasmeasured. The measured value was designated as MFR₄. The results areshown in Table 3.

MFR is an index for the molecular weight, and the greater the MFR, thelower the molecular weight. The fact that both MFR₁ and MFR₄ were lowand the difference therebetween was low indicates that the decrease ofthe molecular weight due to oxidative degradation in the extruder wassmall. This means that the antioxidant worked effectively.

                                      TABLE 3                                     __________________________________________________________________________    Application                                                                         Illustrative                                                                          Comparative                                                     Example                                                                             Compound No.                                                                          Example                                                                              Antioxidant              MFR.sub.1                                                                         MFR.sub.4                   __________________________________________________________________________                  1      None                     12.5                                                                              50 or more                                2      4,4'-butylidenebis(2-tert-butyl-5-methylphenol)                                                        7.2 13.5                                      3      Tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)pro-                                                     6.5 12.2                                             pionyloxymethyl]methane                                  1      1             Bis[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)pro-                                                      4.0 6.3                                              pyl]3,3'-thiodipropionate                                2      4             Bis[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propyl]                                                       4.6 8.7                                              3,3'-thiodipropionate                                    3     16             Tris[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propyl]                         1                        3.8 5.2                                              1,2,3-propanetricarboxylate                              4     15             Tris[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)pro-                                                     4.2 6.1                                              poxycarbonylmethyl]amine                                 5     18             Tetrakis[2-[3-(3-tert-butyl-2-hydroxy-5-methylphe-                                                     3.8 5.5                                              nyl)propoxycarbonl]ethyloxymethyl]methane                6     20             1,3,5-tris[3-(3-tert-butyl-2-hydroxy-5-methylphe-                                                      3.8 5.2                                              nyl)propoxycarbonyl]benzene                              7     21             1,2,4,5-tetrakis[3-(3-tert-butyl-2-hydroxy-5-methyl-                                                   3.9 5.5                                              phenyl)propoxycarbonyl]benzene                           8     22             1,3,5-tris[3-[2-[3-(3-tert-butyl-2-hydroxy-5-methyl-                                                   3.4 4.2                                              phenyl)propoxycarbonyl]ethylthio]propyl]-1,3,5-tri-                           azine-2,4,6 (1H, 3H, 5H)-trione                          9     23             1,3,5-tris[3-[2-[3-(2-hydroxy-3-(1-methylcyclohexyl)-                         6                        3.4 4.2                                              5-methylphenyl)propyloxycarbonyl]ethylthio[propyl]-                           1,3,5-triazine-2,4,6(1H, 3H, 5H)-trione                  10    27             Tris[2-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)pro-                         .                        3.5 4.5                                              poxycarbonyl]ethylthiol]cyclodecane                      11    29             Tetrakis[3-[4-[3-(tert-butyl-2-hydroxy-5-methylphe-                                                    3.5 4.6                                              nyl)propoxycarbonyl]butylthio]propionyloxymethyl]-                            methane                                                  __________________________________________________________________________

APPLICATION EXAMPLES 12 TO 16 AND COMPARATIVE APPLICATION EXAMPLES 4 TO8

0.10 wt% of the antioxidant as shown in Table 4 was added to a powder ofpropylene-ethylene block copolymer having an intrinsic viscosity of 2.3(measured in tetralin at 135° C.) and containing 13 wt% of ethylene,followed by thorough mixing using a mixer. The powder was pelletized bymelt mixing using a 20 mm diameter extruder (L/D: 20) at a cylindertemperature of 260° C. The pellets were formed into a 0.5 mm thick sheetby compression molding at 230° C. The test piece was heated at 150° C.in a circulating air oven. The time required for the test piece to colorbrown due to oxidative degradation was measured. The results are shownin Table 4.

                                      TABLE 4                                     __________________________________________________________________________                                                   Thermal Aging                  Application                                                                         Illustrative                                                                          Comparative                      Resistance                     Example                                                                             Compound No.                                                                          Example                                                                              Antioxidant               (hours)                        __________________________________________________________________________                  4      None                      0.5 or less                                  5      2,6-di-tert-butyl-4-methylphenol                                                                        1 or less                                    6      2,2'-methylenebis(6-tert-butyl-4-methylphenol)                                                           17                                          7      4,4'-butylidenbis(2-tert-butyl-5-methylphenol)                                                           16                                          8      1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)-                                                       36                                                 butane                                                   12     1             Bis[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propyl]                                                    283                                                 3,3'-thiodipropionate                                    13     4             Bis[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propyl]                                                        284                                                 3,3'-thiodipropionate                                    14    16             Tris[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propyl]                                                   208                                                 1,2,3-propanetricarboxylate                              15    27             Tris[2-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)pro-                                                   388                                                 poxycarbonyl]ethylthio]cyclodecane                       16    21             1,2,4,5-tetrakis[3-(3-tert-butyl-2-hydroxy-5-methyl-                                                    263                                                 phenyl)propoxycarbonyl]benzene                           __________________________________________________________________________

EXAMPLE 18 Calciumbis[3-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propylthio]propionate](IllustrativeCompound No. 37)

Into a 500 ml three-neck flask were charged 7.25 g (20.6 mmol) of3-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)propylthio]propionic acid, 0.76g (10.3 mmol) of calcium hydroxide and 200 ml of water, followed byheating and refluxing for about 5 hours.

After the completion of the reaction, water was distilled away and theresidual white solids were washed with a small amount of methanol. Thus,7.65 g (10.3 mmol) of the desired product was obtained. The yield was100%. The physical properties of the product are shown below.

(1) Melting point: 230° C.

(2) ¹ H-NMR CDCl₃ δ[ppm] 1.28 (9H, s), 1.42 (9H, s), 1.95 (2H, tt),2.40-3.09 (8H, m), 6.95 (1H, d), 7.13 (1H, d).

(3) IR: KBr tablet, wavenumber [cm⁻¹ ] 3400, 2950, 1550, 1440, 1410,1190, 870.

EXAMPLE 19 Methyl3-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propylthio]propionate(Illustrative Compound No. 39)

Into a 1 liter four-neck flask were charged 50.00 g (161.1 mmol) of3-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propylthio]propionic acidand 500 ml of methanol. After complete dissolution, 1 ml of conc.sulfuric acid was added. The atmosphere in the reactor was replaced withdry nitrogen, and the reactants were heated and refluxed for about 5hours.

After the completion of the reaction, methanol was removed under reducedpressure. After separation by silica gel chromatography (solvent:chloroform), 49.63 g (153.0 mmol) of the desired product was obtained.The yield was 95%. The physical properties of the product are shownbelow.

(1) ¹ H-NMR CDCl₃ δ[ppm] 1.40 (9H, s), 1.95 (2H, tt), 2.23 (3H, s),2.50-3.10 (8H, m), 3.66 (3H, s), 5.42 (1H, s), 6.72 (1H, d), 6.89 (1H,d).

(2) IR * NaCl, wavenumber [cm⁻¹ ] 3500, 2950, 1740, 1595, 1440, 1220,1170, 1020, 860, 765.

(3) MS: m/e (relative intensity) 324 (30, M⁺), 204 (50), 189 (100), 161(30).

EXAMPLES 20 TO 22

The compounds as shown in Table 5 were synthesized according to themethod used in Example 19. Their structures were confirmed by means ofNMR spectrums, IR spectrums and MS spectrums.

                                      TABLE 5                                     __________________________________________________________________________                             Reactions product                                                             Illus-                                               Reactants                trated      Physical properties of reaction                                               product                                  Ex-                                                                              Compound              com-                                                                              Yield                IR NaCl                                                                              MS m/e               am-                                                                              of Formula                                                                             Compound of                                                                            (g) pound                                                                             (g) Yield            wavenumber                                                                           relative             ple                                                                              (VII) (ml)                                                                             Formula (VI)                                                                           (mmol)                                                                            No. (mmol)                                                                            (%) .sup.1 H--NMR CDCl.sub.3 δ                                              (ppm)        (cm.sup.-1)                                                                          intensity            __________________________________________________________________________    20 Methanol                                                                            500                                                                              3-[3-(3,5-di-                                                                          51.00                                                                             40  49.52                                                                             93  1.28(9H,s), 1.42(9H,s),                                                                    3520,                                                                                366(6,M.sup.+)                   tert-butyl-2-                                                                          (144.7) (135.1) 1.95(2H,tt), 2.40-3.09                                                                     1740,                                                                                351(3),                          hydroxyphenyl)-          (8H,m), 3.68(3H,s),                                                                        1440,                                                                                246(40),                         propylthio]-             (1H,s), 6.95(1H,d),                                                                        1020,                                                                                231(100),                        propionic acid           (1H,d).      765.   57(60).              21 Methanol                                                                            500                                                                              3-[3-[2-hydroxy-                                                                       45.00                                                                             41  43.69                                                                             93  1.25-2.20(10H,m),                                                                          3500,                                                                                364(5,M.sup.+)                   5-methyl-3-(1-                                                                         (128.4) (119.7) 1.33(3H,s), 1.91(4H,tt),                                                                   1730,                                                                                244(100),                        methylcyclohex-          2.26(3H,s), 2.54-2.85                                                                      1440,                                                                                299(40),                         yl)phenyl]propyl-        (8H,m), 3.71(3H,s),                                                                        1245,                                                                                201(30),                         thio]propionic           5.56(1H,s), 6.77(1H,d),                                                                    1160,                                                                                175(20),                         acid                     6.96(1H,d).  760.   161(60),                                                                      147(40),                                                                      97(40),                                                                       55(50).              22 Ethanol                                                                             500                                                                              3-[3-(3-tert-                                                                          50.00                                                                             42  48.55                                                                             89  1.23(H,t), 1.40(9H,s),                                                                     3470, 2930,                             butyl-2-hydroxy-                                                                       (161.1) (143.4) 1.93(2H,tt), 2.23(3H,s),                                                                   1730, 1585,                             5-methylphenyl)-         1.36-3.00(8H,m), 4.13                                                                      1440, 1165,                             propylthio]pro-          (2H,q), 5.47(1H,s),                                                                        1020, 885,                              pionic acid              6.75(1H,d), 6.90(1H,d).                                                                    760.                        __________________________________________________________________________

EXAMPLE 23Tetrakis[3-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propylthio]propionyloxymethyl]methane(Illustrative Compound No. 57)

Into a 50 ml reactor equipped with a condenser, thermometer and nitrogenintroducing thin tube were charged 11.00 g (33.90 mmol) of methyl3-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propylthio]propionate, 0.92g (6.78 mmol) of pentaerythritol and 20 ml of N,N-dimethylformamide. Thepressure in reaction system was reduced to 20 mmHg and 75 vol% (15 ml)of N,N-dimethylformamide was distilled away to dry the reactants,solvent and apparatus. The reaction system was cooled to roomtemperature, and the vacuum was broken by introducing dry nitrogen. 0.02g (2.52 mmol) of lithium hydride was immediately added to initiate theester exchange reaction. The reaction system was heated at 50° to 60° C.under 20 mmHg for 2 to 3 hours, and then heated at 60° to 80° C. under20 mmHg for 2 to 3 hours while distilling N,N-dimethylformamide.Thereafter, the reaction mixture was further heated at 100° to 120° C.under 5 mmHg for 2 to 3 hours. When the reaction was completed, thereaction product was neutralized with dilute hydrochloric acid and thenchloroform was added. After liquid separation and dehydration withanhydrous sodium sulfate, the organic solvent was removed under reducedpressure. After separation by silica gel column chromatography (solvent:chloroform), there was obtained 7.05 g (5.40 mmol) of the desiredproduct. The yield was 80%. The physical properties of the product areshown below.

(1) ¹ H-NMR CDCl₃ δ[ppm] 1.39 (36H, s), 1.91 (8H, tt), 2.22 (12H, s),2.36-3.01 (32H, m), 4.16 (8H, s), 5.42 (4H, s), 6.73 (4H, d), 6.90 (4H,d).

(2) IR: NaCl wavenumber [cm⁻¹ ]3500, 2930, 1735, 1595, 1440, 1214, 1165,1020, 860, 750.

EXAMPLES 24 TO 38

The compounds as shown in Table 6 were synthesized according to themethod used in Example 23. Their structures were confirmed by means ofNMR spectrums, IR spectrums, MS spectrums and elemental analyses.

    TABLE 6      Reaction product  Reactants  Yield  Physical properties of reaction     product  Compound of (g) Methyl ester of (g) Illustrated (g) Yield  IR     NaCl wavenumber MS m/e Elemental Example Formula (VII) (mmmol) Formula     (VI) (mmol) compound No. (mmol) (%) .sup.1 H--NMR CDCl.sub.3 δ     (ppm) (cm.sup.-1) relative intensity analysis       24 Octadecanol 14.99 Methyl 3-[3- 9.00 43 14.23 91 0.70-2.20(37H,m),     3490, 2900,   (55.42) (3-tert-butyl- (27.74)  (25.28)  1.37(9H,s), 1730,     1590,    2-hydroxy-5-     2.23(3H,s), 1460, 1355,    methylphenyl)-     2.35-3.00(8H,m), 1170, 855,    propylthio]-     4.06(2H,t), 760, 720.     propionate     5.47(1H,s),         6.72(1H,d),         6.86(1H,d). 25     Octadecanol 13.30 Methyl 3-[3- 9.00 46 13.37 90 0.71-2.20(37H,m), 3510,     2940,   (49.17) (3,5-di-tert- (24.55)  (22.10)  1.28(9H,s), 1730, 1590,       butyl-2-hy-     1.42(9H,s), 1450, 1355,    droxyphenyl)-     2.40-3.09(     8H,m), 1170, 860,    propylthio]-     4.05(2H,t), 760.    propionate     5.44(1H,s),         6.96(1H,d),         7.14(1H,d). 26 Octadecanol 15.00     Methyl 3-[3-  47  92 0.70-2.20(50H,m), 3500, 2900,   (55.45) (5-tert-buty     l- (27.73)  (25.51)  1.28(9H,s), 1730, 1590,    2-hydroxy-3-     2.37-3.08(8H,m), 1460, 1355,    (1-methylcyclo-     4.06(2H,t), 1165,     860,    hexyl)phenyl]-     5.46(1H,s), 760.    propylthio]-     7.00(1H,d     ),    propionate     7.18(1H,d). 27 Octadecanol 15.00 Methyl 3-[3-  48     96 0.69-2.20(63H,m), 3510, 2900,   (55.45) [2-hydroxy-3,5- (27.73)     (26.34)  2.36-3.05(8H,m), 1730, 1590,    bis(1-methyl-     4.05(2H,t)     1450, 1355,    cyclohexyl)-     5.45(1H,s), 1170, 860,    phenyl]propyl-         7.01(1H,d), 765.    thio]propionate     7.19(1H,d). 28 2,2,6,6- 3.46     Methyl 3-[3- 7.14 52 3.50 35 0.90-2.20(18H,m), 3500, 2950, 449(10,M.sup.+     ) See  tetramethyl- (22.00) (3-tert-butyl- (22.00)  (7.78)  1.40(9H,s),     1730, 1590, 140(30) Note 1  4-piperidin-  2-hydroxy-5-     2.21(3H,s),     1440, 1360, 124(100)  ol  methylphenyl)-     2.30-3.01(8H,m), 1240,     1170,    propylthio]-     5.20(1H,m), 1010, 860,    propionate     5.50(1H,s), 765.         6.71(1H,d),         6.89(1H,d). 29 Pentaery-     1.85 Methyl 3-[3- 19.94 58 16.03 90 1.31(36H,s), 3450, 2950,  thritol     (13.59) (3,5-di-tert- (54.40)  (10.87)  1.45(36H,s), 1740, 1600,     butyl-2-hydrox-     2.00(8H,tt), 1480, 1360,    yphenyl)propyl-     2.40-3.10(32H,m), 1200, 1140,    thio]propionate     4.25(8H,s), 1030,     880,         5.52(4H,s), 760.         7.00(4H,d),         7.21(4H,d). 30     Pentaery- 0.93 Methyl 3-[3- 10.00 59 7.65 76 0.8-2.3(48H,m) 3500, 2900,     thritol (6.86) [2-hydroxy-5- (27.43)  (5.22)  1.30(12H,s) 1735, 1590,     methyl-3-(1-     2.20(12H,s), 1160, 1020,    methylcyclo-     2.3-3.2(32H     ,m), 855, 770.    hexyl)phenyl]     4.19(8H,s),    propylthio]-     5.47(4H,s),    propionate     6.70(4H,d),         6.90(4H,d). 31     2-ethyl-2- 1.15 Methyl 3-[3- 10.00 61 5.00 58 0.70-1.10(5H,m), 3500,     2950,  (hydroxy- (8.56) (3-tert-butyl- (30.82)  (4.94)  1.40(27H,s)     1740, 1595,  methyl)-1,3-  2-hydroxy-5-     1.95(6H,tt), 1220, 1170,     propane-  methylphenyl)-     2.23(9H,s), 1020, 860,  diol  propylthio]-        2.35-3.00(24H,m), 755.    propionate     4.07(6H,s),         5.47(3H,s     ),         6.74(3H,d),         6.90(3H,d). 32 2-ethyl-2- 1.02 Methyl     3-[3- 10.00 62 7.10 82 0.70-1.10(5H,m), 3470, 2960,  See  (hydroxy-     (7.60) (3,5-di-tert- (27.28)  (6.24)  1.28(27H,s) 1740, 1595,  Note 2     methyl)-1,3  butyl-2-hydrox-     1.41(27H,s), 1190, 1020,  propane-     yphenyl)propyl-     1.95(6H,tt), 880, 765,  diol  thio]propionate     2.35-3.05(24H,m), 725.         4.04(6H,s),         5.44(3H,s),     6.89(3H,d),         7.10(3H,d). 33 2-methyl-2- 1.20 Methyl 3-[3- 10.71     63 6.00 60 1.05(3H,s), 3530, 2960,  See  (hydroxyme- (10.00) (3-tert-buty     l- (33.00)  (6.02)  1.40(27H,s), 1745, 1600,  Note 3  thyl)-1,3-     2-hydroxy-5-     1.95(6H,tt), 1225, 1175,  propanediol  methylphenyl)-       2.23(9H,s), 1030, 865,    propylthio]-     2.35-3.00(24H,m), 760.     propionate     4.04(6H,s),         5.47(3H,s),         6.73(3H,d),       6.90(3H,d). 34 2-methyl-2- 0.90 Methyl 3-[3- 10.00 64 7.06 84 1.04(3H,s     ), 3430, 2950,  (hydroxyme- (7.49) (3,5-di-tert- (27.28)  (6.28)     1.29(27H,s), 1740, 1600,  thyl)-1,3,-  butyl-2-hydrox-     1.42(27H,s),     1190, 1020,  propanediol  yphenyl)propyl-     1.95(6H,tt), 875, 760.     thio]propionate     2.40-3.05(24H,m),         4.05(6H,s),     5.46(3H,s),         6.93(3H,d),         7.14(3H,d). 35 dipenta- 1.09     Methyl 3-[3- 10.00 69 6.60 77 1.37(54H,s), 3420, 2950,  See  erythritol     (4.29) (3-tert-butyl- (30.82)  (3.29)  1.90(12H,tt), 1740, 1600,  Note 4        2-hydroxy-5-     2.22(18H,s), 1170, 1020,    methylphenyl)-     2.35-3.00(48H,m), 860, 765.    propylthio]-     3.41(4H,s),    propionate          5.45(6H,s),         6.72(6H,d),         6.87(6H,d). 36 dipenta-     0.96 Methyl 3-[3- 10.00 70 6.11 71 1.30(54H,s), 3470, 2940,  eryithritol     (3.78) (3,5-di-tert- (27.28)  (2.70)  1.41(54H,s), 1730, 1590,     butyl-2-hydrox-     1.98(12H,tt), 1180, 1020,    yphenyl)propyl-     2.35-3.00(48H,m), 875, 750.    thio]propionate     3.45(4H,s),     4.17(12H,s),         5.49(6H,s),         6.95(6H,d),         7.16(6H,d).     37 dipenta- 1.13 Methyl 3-[3- 14.60 71 4.45 45 1.10-2.2(72H,m), 3470,     2900,  erythritol (4.45) [2-hydroxy-5- (40.05)  (1.98)  1.34(18H,s),     1730, 1590,    methyl-3-(1-     2.25(18H,s), 1160, 1040,    methylcyclo-         2.4-3.2(48H,m), 850, 760.    hexyl)phenyl]-     3.48(4H,s),     propylthio]-     4.21(12H,s),    propionate     5.55(6H,s),     6.78(6H,d),         6.97(6H,d). 38 1,3,5-tris- 1.83 Methyl 3-[3- 8.18 73     4.94 62 1.41(27H,s), 3500, 2900,  (2-hydroxy- (7.01) (3-tert-butyl-     (25.21)  (4.34)  1.95(6H,tt), 1730, 1590,  ethyl)-1,3,5-  2-hydroxy-5-       2.24(9H,s), 1220, 1040,  triazine,2,4,  methylphenyl)-     2.35-3.00(24     H,m), 855, 760.  6(1H,3H,5H)-  propylthio]-     4.00-4.50(12H,m),     trione  propionate     5.46(3H,s),         6.75(3H,d),         6.90(3H,d)     .       Note to Table 6:  (1) C.sub.26 H.sub.43 NO.sub.3 S   Calcd. Found C:     69.47% 69.44% H: 9.65%  9.64% N: 3.11%  3.11% (2) C.sub.66 H.sub.104     O.sub.9 S.sub.3   Calcd. Found C: 69.50% 69.68% H: 9.14%  9.21% (3)     C.sub.56 H.sub.84 O.sub.9 S.sub.3   Calcd. Found C: 67.38% 67.43% H:     8.38%  8.49% (4) C.sub.112 H.sub.166 O.sub.19 S.sub.6   Calcd. Found C:     67.09% 66.96% H: 8.29%

The following Application Examples 17 to 23 demonstrate the antioxidantaction of the compound (III) of this invention.

APPLICATION EXAMPLES 17 TO 20

0.10 wt% of the antioxidant as shown in Table 7 was added to apolypropylene powder having an intrinsic viscosity of 1.9 (measured intetralin at 135° C.) and an isotactic index of 98%, followed by thoroughmixing using a mixer. The polypropylene powder was pelletized by meltmixing using a 20 mm diameter extruder (L/D: 20) at a cylindertemperature of 260° C. The MFR (at 230° C.) of the pellets was measuredaccording to JIS K6758. The measured value was designated as MFR₁. Thepelletizing process was repeated three times under the same conditionsas above, and the MFR (at 230° C.) of the resulting pellets wasmeasured. The measured value was designated as MFR₄. The results areshown in Table 7.

                                      TABLE 7                                     __________________________________________________________________________    Application                                                                         Illustrative                                                                          Comparative                                                     Example                                                                             Compound No.                                                                          Example                                                                              Antioxidant             MFR.sub.1                                                                         MFR.sub.4                    __________________________________________________________________________                  1      None                    12.3                                                                              50 or more                                 2      4,4'-butylidenebis(2-tert-butyl-5-methylphenol)                                                       7.2 13.5                                       3      Tetrakis[3-(3,5-di-tert-butyl-4-hydroxylphenyl)pro-                                                   6.5 12.2                                              pionyloxymethyl]methane                                  17    57             Tetrakis[3-[3-(3-tert-butyl-2-hydroxy-5-methylphe-                                                    4.4 5.6                                               nyl)propylthio]propionyloxymethyl]methane                18    62             1,1,1-tris[3-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)-                                                  4.5 6.2                                               propylthio]propionyloxymethyl]propane                    19    69             Bis[2,2,2-tris[3-[3-(3-tert-butyl-2-hydroxy-5-methyl-                                                 4.1 5.3                                               phenyl)propylthio]propionyloxymethyl]ethyl]ether         20    73             1,3,5-tris[2-[3-[3-tert-butyl-2-hydroxy-5-methylphe-                                                  4.6 7.1                                               nyl)propylthio]propionyloxy]ethyl]-1,3,5-triazine-                            2,4,6(1H, 3H, 5H)-trione                                 __________________________________________________________________________

APPLICATION EXAMPLES 21 TO 23

0.10 wt% of the antioxidant as shown in Table 8 was added to powder ofpropylene-ethylene block copolymer having an intrinsic viscosity of 2.3(as measured in tetralin at 135° C.) and containing 13 wt% of ethylene,followed by thorough mixing using a mixer. The powder was pelletized bymelt mixing using a 20 mm diameter extruder (L/D: 20) at a cylindertemperature of 260° C. The pellets were formed into a 0.5 mm thick sheetby compression molding at 230° C. The test piece was heated at 150° C.in a circulating air oven. The time required for the test piece to colorbrown due to oxidative degradation was measured. The results are shownin Table 8.

                                      TABLE 8                                     __________________________________________________________________________                                                 Thermal Aging                    Application                                                                         Illustrative                                                                          Comparative                    Resistance                       Example                                                                             Compound No.                                                                          Example                                                                              Antioxidant             (hours)                          __________________________________________________________________________                  4      None                    0.5 or less                                    5      2,6-di-tert-butyl-4-methylphenol                                                                      1 or less                                      6      2,2'-methylenebis(6-tert-butyl-4-methylphenol)                                                         17                                            7      4,4'-butylidenbis(2-tert-butyl-5-methylphenol)                                                         16                                            8      1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)-                                                     36                                                   butane                                                   21    58             Tetrakis[3-[3-(3,5-di-tert-butyl-2-hydroxyphenyl)-                                                    200                                                   propylthio]propionyloxymethyl]methane                    22    70             Bis[2,2,2-tris[3-[3-(3,5-di-tert-butyl-2-hydroxy-                                                     200                                                   phenyl)propylthio]propionyloxymethyl]ethyl]ether         23    73             1,3,5-tris[2-[3-[3-(tert-butyl-2-hydroxy-5-methyl-                                                    190                                                   phenyl)propylthio]propionyloxy]ethyl]-1,3,5-tri-                              azine-2,4,6(1H, 3H, 5H)-trione                           __________________________________________________________________________

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A phenol derivative of the formula ##STR91##